Electrochimica Acta 60 (2012) 3140

Contents lists available at SciVerse ScienceDirect

Electrochimica Acta
j our nal homepage: www. el sevi er . com/ l ocat e/ el ect act a
Evaluation of self-healing ability in protective coatings modied with
combinations of layered double hydroxides and cerium molibdate
nanocontainers lled with corrosion inhibitors
M.F. Montemor
a,
, D.V. Snihirova
a
, M.G. Taryba
a
, S.V. Lamaka
a
, I.A. Kartsonakis
b
, A.C. Balaskas
b
,
G.C. Kordas
b
, J. Tedim
c
, A. Kuznetsova
c
, M.L. Zheludkevich
c
, M.G.S. Ferreira
c
a
ICEMS, Instituto Superior Tcnico, Technical University of Lisbon, Av Rovisco Pais, 1049-001 Lisboa, Portugal
b
Sol-Gel Laboratory, Institute of Materials Science, NCSR DEMOKRITOS,153 10 Agia Paraskevi Attikis, Greece
c
CICECO-Department of Ceramics and Glass Engineering, University of Aveiro, Campus Santiago, 3810-193 Aveiro, Portugal
a r t i c l e i n f o
Article history:
Received 2 September 2011
Received in revised form26 October 2011
Accepted 26 October 2011
Available online 23 November 2011
Keywords:
Self healing
Coatings
Nanocontainers
Corrosion
a b s t r a c t
Nowadays, there is a strong demand on the search of thinner, but more effective organic coatings for
corrosion protection of metallic substrates, like galvanised steel, used in the automotive industry. Inorder
to guarantee effective corrosion protection of these coatings, and because chromate-based pigments
cannot be used, one of the most attractive strategies consists on the modication of the organic matrix
with nano-additives lled with corrosion inhibitors, which can be released to the active sites. In this
work, two different nano-additives are explored as potential self-healing materials for the development
of active protective coatings. These additives are layered double hydroxides and cerium molybdate hollow
nanospheres loaded with mercaptobenzothiazole, as a corrosion inhibitor. These additives were added
to epoxy primers, individually, or combining the two nanoadditives in the same layer.
The electrochemical behaviour and the potential of self-healing ability were studied by electrochemical
impedance spectroscopy, scanning vibrating electrode technique and scanning ion-selective electrode
technique. The results reveal that both types of nanocontainers can provide effective corrosion inhibition
on articial induced defects, at different stages of the degradation process. Moreover, the results also
show that there is a synergistic effect concerning corrosion inhibition and self-healing potential when a
mixture of the two nanocontainers is used. The mechanism of self healing is presented and discussed in
terms of effect of organic inhibitor and role of the nanocontainers, including effect of cerium ions released
from cerium molibdate nanoparticles.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Organic coatings are the most common and cost effective
method for corrosion protection of metallic parts in a wide range
of technical applications. One of the main roles of the coating is to
provide corrosion protection by creating a barrier that delays the
corrosion attack of aggressive species. Throughout the last decades
organic coatings have been widely applied for the protection of
several metals with signicant progress in the recent years. How-
ever, despite signicant improvements in anti-corrosion coatings
technologies, problems continue in the long-term protection of
metals inaggressive environments, withvery highcosts. Moreover,
the decrease of the weight of components in the transportation
industry, to reduce fuel consumption and CO
2
emission, are also

Corresponding author. Tel.: +351 218419769; fax: +351 218419771.

E-mail address: mfmontemor@ist.utl.pt (M.F. Montemor).
imposing urgent challenges like the use of lightweight alloys and
thinner coating layers produced by eco-friendly routes. The appli-
cation of thinner coatings demands new strategies to extend their
lifetime and to improve their effectiveness, as for example the
development of smart coatings. Nowadays coatings showing self-
healing ability are emerging as promising technical solutions for
improved durability of painted materials. According to the liter-
ature, [1] in a smart healable material a key property is altered,
in a controlled fashion, in response to the introduction of a pre-
determinedexternal stimulus. This denitioncanalso be appliedto
many materials and several properties, including coatings used for
corrosion protection of metallic parts. Some examples of successful
smart functionalities in organic coatings have been proposed in the
works by White et al. [24] that aimat developing self-healing abil-
ity based on encapsulated polymerising agents, for the self repair
of damaged coating matrix. New synthesis routes and strategies
have been reported, highlighting the potential of smart coat-
ings for corrosion protection. Strengths and weaknesses of these
0013-4686/$ see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2011.10.078
32 M.F. Montemor et al. / Electrochimica Acta 60 (2012) 3140
systems have been discussed as well as scale up and related costs.
A detailed review of this topic and related strategies can be found
elsewhere [4,5].
The development of smart coatings, modied with nanoaddi-
tives, specially designed for the mitigation of the corrosion activity
started in the early 2000s with the addition of inhibitors or sub
micron particles to the coatings [69]. Generally, these works
report an improvement of the corrosion resistance and interesting
self-healing effects. The self healing ability was much improved
with the use of pH sensitive reservoirs, acting as containers for
corrosion inhibitors, as for example inhibitor lled particles or
halloysites [10,11], polyelectrolyte layers [12,13] or pH sensitive
hydroxyapatite particles [14]. The use of inhibitors encapsulated
in nanocontainers is still in its infancy but it is certainly a promis-
ing approach. Another aspect of this technology, not explored so
far and requiring deeper studies, is the use of mixtures of corro-
sion inhibitor containers, sensitive to different stimulus and able
to provide corrosion protection at different stages of the coat-
ing life. This aspect is explored in this work, in which thin epoxy
primer coatings modied with different inhibitor loaded nanocon-
tainers, including their mixtures were studied. The nanocontainers
used in this work are layered double hydroxides (LDH) [15] and
cerium molybdate (CeMo) hollow nanospheres [16], both loaded
with mercaptobenzothiazole (MBT) as a corrosion inhibitor. The
modied coatings were applied on galvanised steel. The assess-
ment of prospective self-healing ability demands for the combined
use of various electrochemical techniques. In this paper we also
intend to highlight the potential of three methods that are essential
for effective assessment of the self-healing ability: electrochemical
impedance spectroscopy (EIS) and the scanning vibrating electrode
technique (SVET) combined with the scanning ion-selective elec-
trode technique (SIET).
The results show how EIS can be powerful as a tool for the
screening of promising smart protective systems and highlight the
relevance of the parameters extracted fromthe EIS analysis to the
understanding of the corrosion behaviour of the smart coatings.
From the impedance results it was possible to assess the impact
of the different additives (including mixtures) in the barrier prop-
erties of the coating. On the other hand, localised electrochemical
techniques give detailed knowledge on the corrosion activity and
self-healing extent in the presence of defects exposing the metal.
The results highlight the different kinetics of inhibitionof eachtype
of additives andthesynergistic effect observedwhenbothadditives
are combined within the same coating.
2. Experimental
2.1. Preparation of the coated materials
Galvanisedsteel samples were coatedwitha model epoxy based
coating (without anti-corrosive pigments or any other functional
additives). Thelms wereappliedwitharoll-coater andthedrylm
thickness is approximately 2m in order to simulate the organic
polymer matrix of anti-corrosion systems used in the automotive
industry.
The coatings were modiedwithnanocontainers lledwithcor-
rosion inhibitor. The following additives were used: layered double
hydroxides and ceriummolybdate hollownanospheres lled with
2-mercaptobenzothiazole (MBT). The preparationof LDHnanocon-
tainers and their physicalchemical properties, including anticor-
rosion performance, are described in detail elsewhere [15]. First,
commercial synthetic hydrotalcite(Mg
2
Al
6
(CO
3
)(OH)
16
4H
2
O) was
calcined at 650

C (2h), to remove carbonate anions from the

structure. The incorporation of MBT was achieved in a subse-
quent step consisting of hydration of the calcined sample, using an
aqueous solution containing 0.1M MBT in anionic form (pH 10).
XRD diffractograms acquired after the calcinationrehydration
treatment showed peaks ascribed to the crystalline structure of
LDHs. The loading content of MBT in the LDH(determined by HPLC)
was found to be 1013wt.%.
The preparationandcharacterisationof the CeMonanoadditives
and the strategies used to encapsulate the inhibitor in these parti-
cles are reported in literature [16]. Summarily, the synthetic route
consists of a two-step process. First of all, templates of anionic
charged polystyrene (PS) spheres were prepared using emulsion
polymerisation. Second, the PS containers were coated via the
solgel method to forma ceriummolybdate layer. Ceriummolyb-
date hollow spheres were obtained after the burn off of the PS
templates inair at 550

C. Furthermore, theobtainedceriummolyb-
date containers were loaded with the corrosion inhibitor MBT,
using saturated solution of MBT in acetone into a sealed container
under vacuumconditions. The containers are hollowwith a size of
23020nm. The CeMo containers were loaded with MBT [16,17].
Two sets of modied coatings were prepared: in one set, the
primer coating was loaded with LDHlled with MBT (LDH/MBT) or
with CeMo lled with the same inhibitor (CeMo/MBT) in 4wt.%. For
the second set of samples, both type of containers were mixed, in
equal weight amounts, to modify the primer layer, i.e. the coating
was modied with a mixture of LDH and CeMo containers (same
amount in total) loaded with the same inhibitor, MBT. The amount
of storedinhibitor is not the same for the modiedcoatings because
the loading capacity of each NC is different. For comparative pur-
poses, reference coatings, i.e. coatings without additives were also
prepared.
The thickness and the morphology of the coatings were deter-
minedusing SEM. AJEOL JSM7001F scanning electronmicroscope
equipped with Oxford light elements EDS detector was used in
these complementary experiments. An electron beam energy of
15keV was applied for SEManalysis.
2.2. Electrochemical studies
All the coated specimens were studied by electrochemical
impedance spectroscopy (EIS) in order to evaluate the effect of
the containers on the barrier properties of the coating. For this
purpose, coated samples were immersed in 0.5M NaCl aqueous
solution. The EIS measurements were performed using a Gamry
FAS2 Femtostat with a PCI4 Controller in a frequency range from
100kHz down to 10mHz. All the spectra were recorded at open
circuit potential, applying 10mV sinusoidal perturbations (rms sig-
nal). A conventional three-electrode cell was used, consisting of
a saturated calomel reference electrode, a coiled platinum wire
as counter electrode and the coated metallic coupon as working
electrode. The area of the working electrode was approximately
3.4cm
2
. The electrochemical cell was placed in a Faraday cage.
The evolution of the corrosion activity and the self-healing pro-
cesses were studied by the SVET and SIET techniques. To guarantee
that the corrosion onset starts exactly at the same time for all the
coatings, a defect was created on the coating prior immersion in
0.05M NaCl (pH 6.5). A more diluted solution was used in this
case, compared to the EIS measurements, in order to delay cor-
rosion activity of the blank samples. With this concentration it is
possible to followthe non-inhibitedsystemfor a periodof time suf-
cient to allow effective comparisons with the inhibited samples.
The defect was created by using a punch machine, which is able to
create a lozenge like defect of approximately 0.2mm side. In this
controlled conditions the defect reaches the Zn layer, but not the
iron substrate.
Acommercial systemfromApplicable Electronics, controlled by
the ASET program (Sciencewares), was used to perform the SVET
and SIET quasi simultaneous measurements as previously reported
[18].
M.F. Montemor et al. / Electrochimica Acta 60 (2012) 3140 33
Insulated PtIr probes (Microprobe, Inc.) with platinum black
deposited on a spherical tip of 15mdiameter was used as vibrat-
ingelectrodefor theSVETsystem. Theprobewas placed1003m
above the surface, vibrating in the planes perpendicular (Z) and
parallel (X) to the samples surface. The amplitude of vibration
was 18m, vibration frequencies of the probe were 124Hz (Z)
and 325Hz (X). Only the vertical component was used for treating
experimental data and calculating total current.
The localised pH measurements were carried out using
pH-selective glass-capillary microelectrodes lled with 4-
nonadecylpyridine-based liquid membrane. The pH-selective
microelectrodes were calibrated using commercially avail-
able pH buffers and demonstrated linear Nernstian response
55.21.0mV/pH in a pH range from 2 to 10. The local activity
of H
+
was detected 505m above the surface. More details
on preparation of the microelectrodes can be found elsewhere
[14,19].
The local pH and ionic current density (i
z
) were mapped on a
2626 grid in a 0.05MNaCl solution under open circuit potential
conditions. Thetimeof acquisitionfor eachSVETandSIETdatapoint
was 0.6 and 2.3s respectively, resulting in a total scan time of about
40min. 813 scans for each sample were recorded every day of
immersion.
Such a massive amount of local ionic current distribution data-
maps can be reduced to one very informative plot demonstrating
evolutionof total cathodic andanodic currents intime. This method
of data treatment was proposed by McMurray and co-workers
[20,21] and used by other groups [22,23]. Total anodic (I
anodic
) and
cathodic (I
cathodic
) ionic current density were calculatedintegrating
i
z
current density distribution across the area of each scan at the
time of the measurement, Eqs. (1) and (2):
I
cathodic
=

xmax
x
min

ymax
y
min
[i
z
(x; y) <0dx]dy (1)
I
anodic
=

xmax
x
min

ymax
y
min
[i
z
(x; y) >0]dxdy, (2)
where the x
max
, x
min
, y
max
and y
min
are the coordinates of the
scannedarea of eachsample. Thus, integrating current density with
units of A/cm
2
andspatial dimensions of scannedarea of m, total
cathodic and anodic currents arising through the scanned area will
be expressed in A.
3. Results and discussion
3.1. Barrier properties of the smart coatings
Fig. 1(a) shows the SEM image obtained on the coating modi-
ed with LDH/MBT. The image reveals a uniform surface without
relevant defects such as holes or cracks. There is no evidence of
formation of LDH agglomerates on the surface of the coating. The
thickness of the coatings was determined by observation of the
cross sections and it was found to be between 2 and 2.2m. An
example, for the coating modied with CeMo/MBT, is presented
in Fig. 1(b). The thickness of the blank coating and of the coating
modied with LDH/MBT was also in the same range. Therefore, the
addition of LDH, the addition of CeMo or the addition of mixed LDH
and CeMo did not change the thickness of the coating and does
not induce the formation of large agglomerates. Near the interface
(Fig. 1(b)) for the CeMo modied coating, some CeMo nanocontain-
ers can be observed. The SEMimages indicate that for thin coatings
it is possible to achieve very effective dispersion of nanocontainers,
without formation of undesirable defects in the coating.
Fig. 2 shows the EIS Bode plots evolution during immersion
in NaCl 0.5M for the samples coated with the blank coating
Fig. 1. SEM images obtained in two samples tested: (a) coating modied with
LDH/MBT and (b) coating modied with CeMo/MBT (cross section).
(no additives), coating modied with LDH/MBT, coating modied
with CeMo/MBT and coating containing a mixture of the two addi-
tives (LDH+CeMo)/MBT. The EIS response for the reference sample
and for the LDH/MBT modied coating is very similar at the early
stages of immersion. In both cases there is a marked capacitive
response, extending in the frequency range from100kHz to 10Hz,
and a resistive response inthe lowfrequency end. The response can
be assigned to the coating capacitance and the resistive response to
the resistance of the electrolyte within the coating pores, respec-
tively. For the systems modied with CeMo/MBT the EIS response
reveals a shorter capacitive range and the lowest impedance values
over the entire frequency domain. Moreover, a new time constant
related to interfacial processes develop in the medium/low fre-
quency range.
The systemconsisting of a mixture of LDH/MBT and CeMo/MBT
revealed impedance values, which are below those of the system
modied with LDH/MBT and above those of the coating modied
with CeMo/MBT.
All the coatings displayed a drop of the impedance values, for
more than one order of magnitude, during the rst 24h of immer-
sion. This drop is consequence of electrolyte uptake that forms
conductivepathways throughthecoating. Simultaneously, thehigh
frequency time constant (related to the coating barrier proper-
ties) shifts to higher frequencies, and for the coating modied
with CeMo, it becomes out of the measured frequency range. This
evolution reveals that the barrier properties are poorest for the
coating modied with CeMo/MBT containers. After 24h of immer-
sion and up to one week of immersion, all the other 3 coatings
presented identical impedance values over the entire frequency
domain, despite the differences in the relaxation times and time
constants, which demanded different equivalent circuits to model
the systemas proposed in Fig. 3.
34 M.F. Montemor et al. / Electrochimica Acta 60 (2012) 3140
Fig. 2. EIS Bode plots obtained for the different coatings after immersion in 3% NaCl for: (a) 1h and (b) 24h.
The impedance spectra were tted using the equivalent cir-
cuits depicted in Fig. 3(a) and (b). Due to the dynamic nature of
these systems, different equivalent circuits were used. For all of
them, capacitances were replaced by a constant phase element
(CPE) which accounts for non-homogeneity of the systems and
therefore deviations fromthe ideal capacitive behaviour. Detailed
explanations of the CPE have been previously reported [24]. The
circuit proposed in Fig. 3(a) is composed of two time constants
in cascade, accounting for the electrolyte resistance (Rs), coating
capacitance and pore resistance (CPE1/R1) and double layer and
surface polarization effects (CPE2/R2). This equivalent circuit has
beenusedtodescribethebehaviour of galvanisedsteel coatedspec-
imens [24]. The one in Fig. 3(b) was used to simulate the results
obtained from24h onwards. It makes use of three time constants:
CPE1/R1 accounts for the coating properties, CPE2/R2 is assigned to
the relaxation processes observed in the mediumfrequency range
and the CPE3/R3 describes the lowfrequency behaviour.
Fig. 4 depicts the evolution of the pore resistance of the coat-
ing (R1) for the various coated samples. This parameter is relevant
because it is related to the barrier properties of the coatings and
ideally should not be affected by the addition of the nanocon-
tainers to a great extent. The evolution of this resistance (R1)
follows the same trend for all the coated samples. At the early
stages of immersion, the highest values, around 110
8
cm
2
,
were measured for the reference coating and for the coating
modied with the LDH/MBT. The lowest values, which are two
orders of magnitude lower (110
6
cm
2
), were observed for the
coating modied with CeMo containers. Within the rst 24h of
Fig. 3. Equivalent circuits used for the tting of the EIS measurements.
immersion all the values dropped below 110
5
cm
2
and con-
tinue to decrease attaining values generally below 110
4
cm
2
.
The lowest values were systematically observed for the coat-
ing modied with CeMo/MBT containers. The admittance of
the constant phase element for the high frequency process
(CPE1) increased with time, by more than one order of magni-
tude, from values around 110
9

1
/cm
2
s
n
to values above
110
8

1
/cm
2
s
n
, or evenhigher (above110
7

1
/cm
2
s
n
for
the coating modied with CeMo containers). The exponent value
of the CPE was typically above 0.9 for all the systems, except for the
one with the mixture (exponent between 0.8 and 0.85).
The evolution of the coating pore resistance highlights some
relevant features: the LDH containers do not damage the barrier
properties of the coating, neither at early nor at later stages of
immersion, revealing that this system has a very good compati-
bility with the epoxy matrix. Moreover, this trend also suggests
good dispersibility of the LDH/MBT containers and the absence of
defects in the coating. On the other hand, the addition of CeMo has
a more negative impact, affecting the earlier barrier properties of
the coating. This may indicate poorer dispersibility and compat-
ibility, the presence of defects or some spontaneous leaching of
inhibitor that can interact negatively with the matrix. However,
neither defects nor large agglomerates could be detected by the
Fig. 4. Evolutionof the coating resistance estimated by tting the highest frequency
time constant.
M.F. Montemor et al. / Electrochimica Acta 60 (2012) 3140 35
Fig. 5. (a) Current density maps obtained on the reference sample after 18h of immersion in 0.05MNaCl; (b) pHmap obtained after 18h of immersion; (c) optical micrograph
of the surface.
SEM/EDS analysis, suggesting that most probably the presence of
preferential pathways was createdbypoorer compatibilitywiththe
polymeric matrix. Nevertheless, the coating prepared with a mix-
tureof bothinhibitors evidencedslightlybetter properties probably
because the total amount of CeMo containers was reduced as it was
partially replaced with LDH, which showed barrier properties very
close to the reference system.
3.2. Corrosion inhibition ability of the smart coatings
EIS is a very powerful technique to investigate the evolution of
the coating properties and corrosion inhibition ability, but it gives
anaverage response of the surface, makingit difcult tounderstand
localised events that occur in small defects formed in the coat-
ing. However, spatially resolved electrochemical techniques have
the great advantage of giving local information, regarding evolu-
tion of the corrosion processes (progress and mitigation) on active
defects of the coating. The ability to inhibit corrosion activity in
small defects created on the coating was investigated by SVET and
SIET. Current density maps and pH maps were taken periodically
on the exposed samples up to 34 days of immersion. In order to
quantify the overall electrochemical activity, the total anodic and
cathodic current densities were calculated integrating the maps of
ionic current density.
For the blank coating, corrosion activity was detected imme-
diately after immersion in the aggressive solution. After 1h of
immersion, the anodic current density measured over the defect
was above 70A/cm
2
and increased continuously with time. The
SVET results obtained after 18h of immersion are depicted in
Fig. 5. The anodic current density attained values near 200A/cm
2
(Fig. 5(a)), revealing strong corrosion activity. The pH near the sur-
face was mapped at the same time over the same area by SIET,
(Fig. 5(b)), and the results show that the pH on the anodic area is
around 5.3, thus revealing dissolution of the exposed Zn.
As local acidicationoccurs only due to the hydrolysis of formed
hydrated cations Zn
(aq)
2+
, their concentration can be estimated
based on the Eq. (4).
Zn Zn
(aq)
2+
+2e

(3)
Zn
2+
(aq)
+nH
2
O [Zn(OH)n]
(2n)
+nH
+
pK
1
hyd
= 7.96 K
1
st
= 1.10 10
6
, (4)
where hydrolysis constant pK
1
hyd
is calculated from stability con-
stant of the Zn(OH)
+
complex K
1
st
. A simple calculation [25] shows
that the local activity of generated Zn
(aq)
2+
corresponding to the
measured pH 5.3 is around 2.510
3
M. In the cathodic areas the
pH increased to values above 6.8.
During the rst 18h of immersion there was a clear degradation
of the coating (Fig. 5(c)) around the original defect. Experiments
were carried only for 24h as after this period the coating was
strongly damaged.
Fig. 6shows the time evolutionof the total currents (bothanodic
and cathodic) for the systemmodied with LDH/MBT. Ideally, inte-
grated cathodic and anodic currents at any given time should be
equal, with overall current being zero:
I
cathodic
= I
anodic
; I
overall
= I
cathodic
+I
anodic
= 0 (5)
However, in practice SVET is not always able to measure all
localised currents. In the case of a coated sample, with a defect,
anodic activityis localisedinthe defect while the cathodic reactions
are partially taking place under the coating. This causes alkalinisa-
tion, with release of OH

, under the coating. The SVET vibrating

probe measures the potential differences arising in solution due to
the ionic uxes produced on the sample surface. Thus, it may not
detect all the activity taking place under the coating, as much of
the OH

ions generated underneath the coating may not be able to

owto the solution. This means that eventhoughthe Eq. (5) is valid
in this case, total cathodic current available for SVET detection will
36 M.F. Montemor et al. / Electrochimica Acta 60 (2012) 3140
Fig. 6. Evolution of the total anodic and cathodic currents obtained integrating
current density distribution for the coating modied with LDH/MBT.
be smaller than total anodic current. On the other hand, there is
a time frame necessary to complete the measurement, and during
this time, the anodic and cathodic currents may suffer some slight
changes, leading to deviations fromthe ideal behaviour.
The rst but weak signs of corrosion activity for the coating
modied with LDH/MBT were detected after 45h of immersion
with a small increase of the corrosion activity over the defect and
a small acidication of the anodic areas. From this time, and up
to 1 day of immersion, there was very little activity, revealing a
strong inhibition effect when compared to the blank coating. After
18h of immersion the pH was 5.5, indicating weaker dissolution
of Zn (Fig. 7). After 1819h of immersion there was an increase
in the corrosion activity characterised by values of current density
that attained 100A/cm
2
after 2 days of immersion, and pHvalues
around 5.4 (SVET-SIET maps are not shown). Despite this increased
activity, the values of the current density were about two times
lower than those obtained for the reference coating. Fromthis time
onwards, the current intensity increased until 3 days of immersion,
time after which the experiment was concluded.
The coating modied with the CeMo/LDH containers shows a
very distinct behaviour: evident corrosion activity was observed
at the early stages of immersion. The pH in the anodic defect
Fig. 8. Evolution of the total anodic and cathodic current obtained integrating cur-
rent density distribution for the coating modied with CeMo/MBT.
reached value 5.04 corresponding to high dissolution rate of Zn
with local Zn
2+
concentration reaching 110
2
M(SIET map is not
shown). The overall anodic current density values reached a max-
imum after 35h of immersion (Fig. 8). However after this peak
activity, the current densities decreased attaining very lowvalues.
The current density map (Fig. 9(a)) obtained after approximately
20h of immersion clearly illustrates this trend: both anodic and
cathodic activities are low and do not exceed 5A/cm
2
. The pH
in the defect increased up to 5.68, corresponding to lower disso-
lution rate of Zn
2+
; approximately 4.410
4
M. This trend was
remained for more than 3 days of immersion. An increase of the
corrosionactivity was observedafter 4days of immersionandcoat-
ing deterioration was detected after one week. Comparatively to
the coating modied with LDH/MBT these results indicate that: (1)
corrosion activity develops much earlier in the CeMo/MBT mod-
ied coating, probably due to the poorest barrier properties; (2)
important corrosion inhibition was observed after a maximum of
corrosion activity; (3) corrosion inhibition extended over a longer
period. This evolution suggests that CeMo/MBT containers are also
effective corrosion inhibitors, acting delayed comparatively to the
LDH/MBT ones.
Fig. 7. Coating modied with LDH/MBT nanocontainers. (a) Current density map obtained after 18h of immersion in 0.05MNaCl; (b) pH map.
M.F. Montemor et al. / Electrochimica Acta 60 (2012) 3140 37
Fig. 9. Coating modied with CeMo/MBT nanocontainers. (a) Current density map obtained after 20h of immersion in 0.05MNaCl; (b) pH map.
When the two types of containers are mixed, the localised elec-
trochemical measurements also reveal a kind of mixed behaviour
(Fig. 10). Thus, corrosion at early stages is delayed, being neg-
ligible (Figs. 10 and 11(a)). The activity over the defect became
evident between 18 and 24h, reaching a maximum value. At this
time the local pH at the anodic sites was around 5.2 (Fig. 11(b)).
Thus, at this stage the behaviour is very similar to that observed
for the LDH/MBT modied coatings inhibition at earlier immer-
sion times and increase of corrosion activity after approximately
18h of immersion. Increased activity in the defect creates the con-
ditions for activating CeMo/MBT containers and for longer times
(2425h onwards), the anodic currents decrease, being negligible
up to 3 days of immersion. This behaviour is nowsimilar to the one
observed for the CeMo/MBT coatings that showed a decrease of the
anodic current anda stabilizationof thepHaround5.66. This trend
was kept for several days of immersion (Figs. 10 and 11(c) and (d)).
The overall anodic current was depicted for the three systems
modied with nanocontainers for better comparison of the SVET
results (Fig. 12). The current values for the blank sample are not
depicted, because they were much higher and because the experi-
ment was stopped after 1 day due to severe damage of the coating.
The evolution of the anodic currents (Fig. 12a) show that for the
mixed systemthere are two steps for the corrosion inhibition pro-
cess, which suggests different kinetics of inhibition and eventually
different mechanisms triggering the corrosion inhibitor. LDH/MBT
Fig. 10. Evolution of the total anodic and cathodic current obtained integrating
current density distributionfor the coating modiedwithLDH/MBT andCeMo/MBT.
delays the corrosion activity at early stages, meaning that these
containers are extremely effective at the onset of the corrosionpro-
cess. This is conrmed by the behaviour of the coating modied
with LDH/MBT only as well. However, contrasting with this one,
in the mixed systemthe overall anodic current started to decrease
after passing a maximum, attaining values very similar to those
observed in the CeMo/MBT modied coatings. In fact, as shown in
Fig. 8 the CeMo/MBT additives start to inhibit the defect only after
several hours of immersion and after some corrosion activity. Thus,
the CeMO/MBT show slower kinetics of inhibition, which start to
predominate in the mixed coating after approximately one day of
immersion. The complementary behaviour of both additives can be
used to create a synergistic effect, in which the combination of the
two delays corrosion onset due to: (1) early inhibitive ability of the
LDH/MBT anddecreases of the longer termcorrosionactivity due to
the slower inhibition ability of CeMo/MBT. This trend suggests that
this combination can be an interesting approach to develop new
smart coatings with self-healing potential and different kinetics of
inhibition. The reasons for the effective self-healing effect observed
relies not in the inhibitor activity only (which is MBT in both cases)
but alsoontheactiveroleof LDHandCeMocontainers. Accordingto
literature [26], the release of MBT fromLDHs proceeds very rapidly
after exposure to NaCl. Thus, a high concentration of inhibitor is
releasedat earlystages intheactivesites. It was showninaprevious
work [26] that after a period of chloride exposure the chemical ion-
exchange equilibrium is attained. The leaching of inhibitor occurs
by anexchange mechanism(release of aninhibitor andentrapment
of aggressive chlorides) and the release of an inhibitor is sequen-
tial, providing protection on demand. Therefore it is expected to
observe an important delay of the corrosion activity because the
chloride ions are trapped by the LDH and because the released
MBT inhibits corrosion onset. For longer immersion times, there
is an excess of chloride ions and the amount of released inhibitor
may decrease, leadingtoanincrease of the anodic current densities.
Nevertheless, the values were less than half of the values observed
in the blank coating, indicating that corrosion inhibition was still
provided by the released inhibitor. In the case of the blank coating
severe deterioration was observed within the rst day, whereas
in the LDH/MBT system the coating lasted for more than 3 days
until relevant deterioration occurs. In addition to the chloride trap-
ping effect, the inhibitionof corrosionactivity, comparatively tothe
blank system, involves the formation of a protective inhibitor layer
over the attacked surface. The effectiveness of MBT and thiazoles as
38 M.F. Montemor et al. / Electrochimica Acta 60 (2012) 3140
Fig. 11. Coating modied with a mixture of LDH/MBT and CeMO/MBT nanocontainers. Current density maps obtained after different immersion times in 0.05M NaCl: (a)
after 3h, (b) after 18h, (c) after 40h and (d) optical image after 7 days.
corrosion inhibitors has been demonstrated for zinc, steel [2729]
and aluminium[30,31] and the mechanismis suggested to involve
the formation of inhibitive adsorption layers.
The inhibitive effect of CeMo/MBT may also rely on the con-
tainers behaviour and on inhibitor activity. According to previous
literature, CeMo empty containers have a positive effect in protect-
ing aluminiumsubstrates [16]. Literature [32] also points out that
cerium molybdates can work as ion exchangers and that they are
sensitive topHbeing stable inalkaline environment andable todis-
solve in more acidic conditions. If the inhibitor could be released
due to instability of CeMo, in the more acidic environment cre-
ated in the anodic areas, this would explain the drop observed after
corrosion activity peaks. However the exact mechanismis not clar-
ied as little is known in literature about the exact ion-exchange
properties of these containers. Another possible explanationfor the
self healing effect involves both ceriumand molybdate ions due to
dissolution of the nanocontainers. These particles may suffer disso-
lution in acidic media (formed over the anodic areas) and therefore
release of these ions is likely to occur. Indeed these species can be
used as inhibitive pigments as reported in literature [33]. Therefore
M.F. Montemor et al. / Electrochimica Acta 60 (2012) 3140 39
Fig. 12. Evolution of the total anodic (a) and cathodic (b) current obtained integrat-
ing current densitydistributionfor the coatings modiedwithLDH/MBT, CeMo/MBT
and the mixture (LDH+CeMo)/MBT.
ceriumand/or molybdeniumspecies can be formed on the healed
places, playing an inhibitive role as effective inhibitors reported
in literature [3436]. The results obtained in this work evidence
an effective corrosion inhibition ability of these CeMo/MBT nano
containers that extended over longer periods.
In the present work it is demonstrated that effective inhibi-
tion of the corrosion processes in articially induced defects can be
achieved by the addition of LDHand CeMo loaded with MBT as cor-
rosioninhibitor. The results highlight, bythe rst time, a synergistic
effect onthe self-healing ability potential of mixtures of containers,
withdifferent kinetics of inhibitor release, acting as smart additives
for organic coatings.
4. Conclusions
Modication of epoxy based coatings with layered
double hydroxides anion-exchange containers lled with 2-
mercaptobenzothiazole has no negative impact on the barrier
properties of thin epoxy coatings. However, modication of the
same epoxy matrix with ceriummolybdate nanoparticles induces
some losses in terms of barrier properties.
The ability of layered double hydroxides ion exchange contain-
ers lled with mercaptobenzothiazole to inhibit corrosion activity
in defects formed in the epoxy coating was demonstrated by the
scanning vibrating probe and ion-selective electrode techniques.
These additives delay corrosiononset, being very effective at earlier
immersion stages.
Cerium molybdate hollow nanospheres lled with 2-
mercaptobenzothiazole show very good inhibition potential
after a period of relevant corrosion activity. The corrosion activity
is effectively inhibited for longer immersion times and can be
attributed either to the organic inhibitor or release of active
species, such as ceriumions fromthe nanocontainers, themselves.
The addition of a mixture of nanocontainers, lled with 2-
mercaptobenzothiazole, results in a synergistic inhibition effect
that combines early corrosion protection and longer term inhibi-
tion. This is related to the different activation mechanism of the
containers. Such behaviour clearly demonstrates the potential of
nanocontainers mixtures todesignsmart coatings withself-healing
ability for prolonged coating lifetime.
Acknowledgments
The authors acknowledge the MUST (NMP3-LA-2008-214261)
project, fundedbythe FP7programme andall the partners that pro-
vided contributions to this work: Production of model coatings: Mr
Thomas-Schmidt-Hansberg and Valerie Gandubert fromChemetall
andtheir team; discussions withprof. Grundmeier andhis group. A.
Salak is acknowledged for XRDmeasurements on LDHs. Support by
Portuguese Foundation for Science and Technology (FCT) through
the project PTDC/CTM/108446/2008 is also acknowledged. D.V.S.
and M.G.T. thank their personal FCT grants SFRH/BD/72497/2010
and SFRH/BD/72602/2010. J. Tedim thanks FCT for Post-Doctoral
grant (Ref. SFRH/BPD/64335/2009).
References
[1] E.B. Murphy, F. Wudl, Prog. Polym. Sci. 35 (2010) 223.
[2] B.J. Blaiszik, N.R. Sottos, S.R. White, Compos. Sci. Technol. 68 (2008) 978.
[3] J.D. Rule, E.N. Brown, N.R. Sottos, S.R. White, J.S. Moore, Adv. Mater. 17 (2005)
205.
[4] B.J. Blaiszik, S.L.B. Kramer, S.C. Olugebefola, J.S. Moore, N.R. Sottos, S.R. White,
Annu. Rev. Mater. 40 (2010) 179.
[5] S. Zwaag, Self-healing Materials An Alternative Approach to 20 Centuries of
Materials Science, Springer, The Netherlands, 2007.
[6] N. Voevodin, N.T. Grebasch, W.S. Soto, F.E. Arnold, M.S. Donley, Surf. Coat.
Technol. 140 (2001) 24.
[7] M.G.S. Ferreira, R.G. Duarte, M.F. Montemor, A.M.P. Simes, Electrochim. Acta
49 (2004) 2927.
[8] S.V. Lamaka, M.L. Zheludkevich, K.A. Yasakau, M.F. Montemor, P. Cecilio, M.G.S.
Ferreira, Electrochem. Commun. 8 (2006) 421.
[9] K. Aramaki, Corros. Sci. 47 (2005) 1285.
[10] D.G. Shchukin, Mi. Zheludkevich, K. Yasakau, S. Lamaka, M.G.S. Ferreira, H.
Mhwald, Adv. Mater. 18 (2006) 1672.
[11] D.G. Shchukin, S.V. Lamaka, K.A. Yasakau, M.L. Zheludkevich, H. Mhwald,
M.G.S. Ferreira, J. Phys. Chem. C 112 (2008) 958.
[12] D.G. Shchukin, H. Mohwald, Small 3 (2007) 926.
[13] S.V. Lamaka, D.G. Shchukin, D.V. Andreeva, M.L. Zheludkevich, H. Mhwald,
M.G.S. Ferreira, Adv. Funct. Mater. 18 (2008) 3137.
[14] D. Snihirova, S.V. Lamaka, M. Taryba, A.M. Salak, S. Kallip, M.L. Zheludkevich,
M.G.S. Ferreira, M.F. Montemor, ACS Appl. Mater. Interfaces 2 (11) (2010) 3011.
[15] M.L. Zheludkevich, S.K. Poznyak, L.M. Rodrigues, D. Raps, T. Hack, L.F. Dick, T.
Nunes, M.G.S. Ferreira, Corros. Sci. 52 (2010) 602.
[16] I.A. Kartsonakis, G. Kordas, J. Am. Ceram. Soc. 93 (1) (2010) 65.
[17] I. Kartsonakis, I. Daniilidis, G. Kordas, J. Sol-Gel Sci. Technol. 48 (2008) 24.
[18] S.V. Lamaka, M. Taryba, M.F. Montemor, H.S. Isaacs, M.G.S. Ferreira, Elec-
trochem. Commun. 13 (2011) 20.
[19] M. Taryba, S.V. Lamaka, D. Snihirova, M.G.S. Ferreira, M.F. Montemor, W.K.
Wijting, S. Toews, G. Grundmeier, Electrochim. Acta 56 (2011) 4475.
[20] H.N. McMurray, D. Williams, D.A. Worsley, J. Electrochem. Soc. 150(2003) B567.
[21] D.A. Worsley, H.N. McMurray, J.H. Sullivan, I.P. Williams, Corrosion 60 (2004)
437.
[22] R.M. Souto, Y. Gonzalez-Garcia, A.C. Bastos, A.M. Simoes, Corros. Sci. 49 (2007)
4568.
[23] M. Yan, V.J. Gelling, B.R. Hinderliter, D. Battocchi, D.E. Tallman, Corros. Sci. 52
(2010) 2636.
[24] (a) J.B. Jorcin, M.E. Orazem, N. Pbre, B. Tribollet, Electrochim. Acta 51 (2006)
1473;
(b) W. Trabelsi, E. Triki, L. Dhouibi, M.G.S. Ferreira, M.L. Zheludkevich, M.F.
Montemor, Surf. Coat. Technol. 200 (2006) 4240.
[25] S.V. Lamaka, R.M. Souto, M.G.S. Ferreira, in: A. Mendez-Vila, J. Diaz (Eds.),
Microscopy: Science, Technology, Applications and Education, vol. 3, 2010
ed., Formatex Research Center, Badajoz, Spain, 2010, p. 2162, Available on
http://www.formatex.info/microscopy4/2162-2173.pdf.
[26] S.K. Poznyak, J. Tedim, L.M. Rodrigues, A.N. Salak, M.L. Zheludkevich, L.F.P. Dick,
M.G.S. Ferreira, ACS Appl. Mater. Interfaces 1 (2009) 2353.
[27] J.V. Custdio, S.M.L. Agostinho, A.M.P. Simes, Electrochim. Acta 55 (2010)
5523.
[28] K.F. Khaled, M.A. Amin, Corros. Sci. 51 (2009) 1964.
40 M.F. Montemor et al. / Electrochimica Acta 60 (2012) 3140
[29] A.A. Al-Sarawy, A.S. Fouda, W.A. Shehab El-Dein, Desalination 15 (2008) 279.
[30] S.V. Lamaka, M.L. Zheludkevich, K.A. Yasakau, M.F. Montemor, M.G.S. Ferreira,
Electrochim. Acta 52 (2007) 7231.
[31] M.L. Zheludkevich, K.A. Yasakau, S.K. Poznyak, M.G.S. Ferreira, Corros. Sci. 47
(2005) 3368.
[32] A. Nilchi, B. Maalek, A. Khanchi, M. Ghanadi Maragheh, A. Bagheri, Radiat. Phys.
Chem. 75 (2006) 301.
[33] K. JanardhananSreeram, R. Srinivasan, J. Meena Devi, B. Unni Nair, T. Ramasami,
Dyes Pigments 75 (2007) 687.
[34] C.G. da Silva, I.C.P. Margarit-Mattos, O.R. Mattos, H. Perrot, B. Tribollet, V. Vivier,
Corros. Sci. 51 (2009) 151.
[35] K. Aramaki, Corros. Sci. 43 (2001) 2201.
[36] N.C. Rosero-Navarro, M. Curioni, Y. Castro, M. Aparicio, G.E. Thompson, A.
Durn, Surf. Coat. Technol. 206 (2011) 257.